2,4,7-Decatrienal as perfuming or flavoring ingredient

ABSTRACT

Compounds of formula  
                 
 
     wherein the double bond in position 4 has a cis or trans configuration, or a mixture of these compounds, are useful as perfuming or flavoring ingredients, in particular as a booster for mandarin or tangerine type flavors.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of the U.S. national phasedesignation of International Application PCT/IB00/01936 filed Dec. 20,2000, the entire content of which is expressly incorporated herein byreference thereto.

TECHNICAL FIELD

[0002] The present invention relates to the flavor and fragranceindustry. It concerns more particularly the use, as a perfuming orflavoring ingredient, of a compound of formula

[0003] wherein the double bond in position 4 has a cis or transconfiguration, or of a mixture of these compounds.

BACKGROUND ART

[0004] The compound of formula (I) is known from the prior art. Severalauthors have in fact identified 2,4,7-decatrienal formed in naturalcompounds during the oxidative degradation of unsaturated fatty acids.For example, R. Tressl et al. in J. Agric. Food Chem., 1977, Vol. 25, p.459, have identified 2,4,7-decatrienal among the constituents of cookedasparagus, with the compound being formed following the degradation offatty acids. Previously, other authors had also identified this compoundas a product derived from the degradation of linolenic acid, in cookedchicken (Harkes et al., J. Am. Oil Chem. Soc., 1974, Vol. 51, p. 356),as well as in mackerel oil (Ke et al., J. Am. Oil Chem. Soc., 1975, Vol.52, p. 349) or in French fries (Buttery et Ling, J. Agric. Food Chem.,1972, Vol. 20, p. 698). Following these identifications,2,4,7-decatrienal was synthesised. In particular, J. Am. Oil Chem. Soc.,1972, Vol. 49, p. 555 discloses the synthesis of (2E,4E,7Z)-,respectively (2E,4Z,7Z)-2,4,7-decatrienal. Moreover, the latter documentdescribes the characteristic odor of each one of its isomers. Inparticular, the odors of the latter have been described as being fishy,with the authors further concluding that 2,4,7-decatrienal wasresponsible for the typical fishy smell associated with oxidizedlinolenic acid. These fishy odors characterising the aldehyde aredescribed as off-notes, that is to say as unpleasant, undesirable oreven repulsive notes.

SUMMARY OF THE INVENTION

[0005] The present invention relates to a process to confer, improve,enhance or modify the mandarin or tangerine character of a compositionor product, wherein a perceptible amount of the compound of formula (I)

[0006] wherein the double bond in position 4 has a cis or transconfiguration, or of a mixture of these compounds, is added to thecomposition or product.

[0007] It has now unexpectedly been found that 2,4,7-decatrienal, in theform of one of its isomers of the (2E,4Z,7Z) or (2E,4E,7Z)configuration, or in the form of a mixture of these isomers, could beadvantageously used in the flavoring of usually flavored compositions orconsumer products. This is particularly surprising given that, asmentioned above, this compound was until now known as a degradationproduct of a natural product, responsible for undesirable and repulsiveoff-notes.

[0008] The inventors have now been able to establish that, contrary toall expectations, this compound possesses very interesting flavoringproperties, and that it develops, in particular in some specificcompositions, gustatory notes which are particularly useful for thereconstitution of flavors of the mandarin or tangerine type, to which itconfers a very natural character.

[0009] The present invention also relates to the use as a perfuming orflavoring ingredient of a compound of formula

[0010] wherein the double bond in position 4 has a cis or transconfiguration, or of a mixture of these compounds.

[0011] The compounds of the invention develop a fishy aromatic top note,more or less fatty and oily, depending on the specific compoundselected.

[0012] Among the compounds of formula (I), (2E,4Z,7Z)-2,4,7-decatrienalis particularly appreciated. In fact, this isomer possesses a verypowerful flavor and develops, besides the fishy note, a linseed oil typenote, which can be advantageously used in applications in compositionsas shown below. Moreover, the mixtures of (2E,4Z,7Z)-2,4,7-decatrienaltogether with (2E,4E,7Z)-2,4,7-decatrienal, containing a preponderantamount of (2E,4Z,7Z)-2,4,7-decatrienal, are also very much appreciatedaccording to the invention. In particular, the mixtures comprising atleast 75% of (2E,4Z,7Z)-2,4,7-decatrienal, are preferred. These mixturesdevelop a multi-varied aromatic note, wherein the fishy and oilycharacters are represented, but together with green, fruity, woody,melon, linseed oil, olive oil, cucumber or kiwi notes.

[0013] Besides their very interesting flavor, the compounds of theinvention also provide a fatty and round mouthfeel, which may beadvantageously used for the flavoring of a large number of products.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In a general manner, the use of the compounds of formula (I)proves to be advantageous in all flavoring compositions of the citrustype. More particularly, their use is very well appreciated in flavoringcompositions of the mandarin or tangerine type, wherein they can be usedas boosters or reinforcing agents for this type of flavor. In fact,thanks to the presence of their oily and fishy notes, the compounds ofthe invention, distinctively characterize these mandarin/tangerine typeflavors with respect to namely orange type flavors. Moreover, thevariety of the other notes presented by these compounds, such as citrus,melon, green or kiwi notes, confers to the compositions to which theyare added a very natural taste as well as a reinforcement of their pulpyand juicy character. Finally, they confer to these compositions amouthfeel which renders the flavor complete.

[0015] According to one embodiment of the invention, a compound offormula (I) may be admixed with (Z)-4-dodecenal before being added to aflavoring composition, preferably one of the mandarin or tangerine type.In fact, the association of both compounds intensifies the juicy, greenand citrus character of such a composition, while preserving its oilyand fatty character, making it thus possible to obtain a very naturalflavoring composition. Typical amounts of (Z)-4-dodecenal in suchcompositions can vary from 0.05 to 0.4% by weight relative to the weightof the composition.

[0016] It goes without saying that the compounds of the invention canalso be advantageously used in other types of flavoring or flavoredcompositions. One can cite as example their positive effect when addedto compositions of the fruity type, and namely of the tropical fruittype, which are rendered more juicy, natural and fresh, and the fruitycharacter of which is reinforced.

[0017] In a general manner, the oily, fishy character of the compoundsof the invention can be advantageously used in applications such asbeverages, in particular teas, and in oily, green, fruity and tropicaltype flavors.

[0018] The value of the compounds of the invention as flavoringingredients is all the more important in that, although their aromatictop note is very powerful, a large number of sub-notes also presentprovides an unexpected positive effect in the compositions to which theyare added.

[0019] The concentrations in which the compounds of formula (I) can beadded to the flavoring compositions and to the products that have to beflavored in order to impart the cited effects vary in a large range ofvalues, which may range from 0.01 ppm to 0.5 ppm or even to 1 ppm, withrespect to the weight of the final product in which they areincorporated. These concentrations notably depend on the nature of theisomer or of the mixture used. For instance, as(2E,4Z,7Z)-2,4,7-decatrienal is more powerful than its isomer, or eventhan a mixture of isomers, it will generally be used in lowerconcentrations than those cited.

[0020] The compounds of the invention can be useful for the flavoring ofvaried consumer products such as foods, beverages, chewing-gums,toothpastes or pharmaceutical preparations.

[0021] Examples of foods or beverages susceptible of being flavoredinclude ice creams, dessert creams, yogurts, dairy products in general,confectionery products, syrups, teas, cooked sugars, or marmalades.

[0022] The compounds of the invention are incorporated in foods,beverages, chewing-gums or pharmaceutical preparations to be flavored,according to usual processes in the art, either alone, or in admixturewith other natural or synthetic flavoring ingredients, such as forinstance (Z)-4-dodecenal mentioned above. They can be used as such or insolution in usual edible solvents such as triacetin, ethylic alcohol orpropylene glycol, or in admixture on a solid support, for example adextrin or gum arabic.

[0023] Moreover, it has been noticed that the compounds of the inventionare also useful in the field of perfumery. They possess an odor, thelinseed oil note of which is more perceptible than the aldehydeconnotation. Furthermore, they present a very natural mandarin note.

[0024] The compounds of the invention can be advantageously used in fineperfumery, as well as in functional applications, for the preparation ofperfuming compositions and perfumed products. Among the latter, one cancite perfumes and Colognes, soaps, shower or bath gels, shampoos andother hair-care products, cosmetic preparations and body deodorants orair fresheners. They can also be useful in the perfuming of detergentsfor textiles and dishes, fabric softeners and household products.

[0025] When they are used for these applications, interesting olfactoryeffects can be obtained using low concentrations, and the skilled personin the art is able to choose the compounds as a function of the natureof the product that has to be perfumed and of the perfume intensitydesired.

[0026] Their odor proves to be also very powerful. Therefore, they canbe used in even very diluted concentrations, such as for instance about0.01% by weight and can range up to 0.6% by weight or more, depending onthe type of application.

[0027] In these applications, the compounds of the invention can be usedeither alone, or in admixture with perfuming co-ingredients, solvents oradjuvants of current use in the art. A more detailed citation of theseco-ingredients would be superfluous here, the skilled person in the artbeing able to select them on the basis of his experience and withinspiration from reference texts such as the S. Arctander's book,Perfume and Flavor Chemicals, Montclair, N.J. (1969) or more recentversions thereof.

EXAMPLES

[0028] The invention will now be described in a more detailed manner, inthe following examples, wherein the abbreviations have the usual meaningin the art.

Example 1: Preparation of the Compounds of Formula (I)

[0029] The processes for the preparation of (2E,4Z,7Z)-, respectively(2E,4E,7Z)-decatrienal, are described by P. Meijboom et al. in J. Am.Oil Chem. Soc., 1972, Vol. 49, p. 555. The content of this document isexpressly incorporated herein by reference thereto.

[0030] The compounds used according to the present invention presentedthe following analytical characteristics:

[0031] a) (2E,4Z, 7Z)-2,4,7-decatrienal

[0032] MS: 150(3, M⁺ ^(_(·)) ), 135(3), 132(2), 121(26), 117(10),107(15), 103(17), 91(65), 79(100), 67(42), 63(14), 53(37), 39(80),27(41).

[0033]¹H-NMR: 1.00(t, J=8, 3H, C10); 2.10(m, 2H, C9); 3.08(dxd, J₁=8,J₂=8, 2H, C6); 5.35(m, 1H, C7); 5.52(m, 1H, C8); 5.95(dxt, J₁=10, J₂=8,1H, C5); 6.15(dxd, J₁=16, J₂=8, 1H, C2); 6.30(dxd, J₁=10, J₂=10, 1H,C4); 7.48(dxd, J₁=16, J₂=10, 1H, C3); 9.62(d, J=8, 1H, C1).

[0034]¹³C-NMR: 193.8(d); 146.4(d); 141.5(d); 133.7(d); 132.1(d);126.6(d); 124.8(d); 26.6(t); 20.7(t); 14.1(q).

[0035] b) (2E,4E, 7Z)-2,4,7-decatrienal

[0036] MS: 150(6, M⁺ ^(_(·)) ), 135(3), 132(2), 121(30), 117(9),107(16), 103(19), 91(66), 79(100), 67(47), 63(17), 53(42), 39(81),27(42).

[0037]¹H-NMR: 0.97(t, J=8, 3H, C10); 2.08(m, 2H, C9); 2.97(dxd, J₁=8,J₂=8, 2H, C6); 5.35(m, 1H, C7); 5.52(m, 1H, C8); 6.08(dxd, J₁=16, J₂=8,1H, C2); 6.30(m, 2H, C4 and C5); 7.10(dxd, J₁=16, J₂=10, 1H, C3);9.53(d, J=8, 1H, C1).

[0038]¹³C-NMR: 193.8(d); 152.6(d); 144.9(d); 134.2(d); 130.3(d);128.6(d); 124.0(d); 30.8(t); 20.6(t); 14.1(q).

Example 2: Flavoring Composition of the Tangerine Type

[0039] 0.5 ppm of (2E,7Z)-2,4,7-decatrienal (4Z:4E, 75:25) were added toa basic solution of 100 ppm of a tangerine type flavor (N° 727730.01 A;origin: Firmenich SA, Geneva, Switzerland) in acidulous sweetened water(7% sucrose, 0.15% citric acid). The thus obtained flavored compositionand the basic solution were compared on a blind test by a panel ofexpert flavorists. The latter preferred the composition flavoredaccording to the present invention and mentioned in particular that itstaste was more complete, more natural and closer to tangerine than toorange.

Example 3: Tea Type Flavoring Composition

[0040] 0.2 pm of (2E,7Z)-2,4,7-decatrienal (4Z:4E, 75:25) were added toa basic solution of a tea flavor (N° 597.302 T; origin: Firmenich SA,Geneva, Switzerland) (1000 ppm) in acidulous sweetened water (7%sucrose, 0.15% citric acid). The thus obtained flavored composition andthe basic composition were compared on a blind test by a panel of expertflavorists. The latter preferred the composition flavored according tothe present invention, and indicated in particular that it possessed afresher infused flavor, and that its taste was more complete and moreseasoned than that of the basic solution. Moreover, from a mouthfeelpoint of view, the panel of experts noticed that the composition of theinvention was more naturally astringent than the solution lacking in(2E,7Z)-2,4,7-decatrienal.

Example 4: Kiwi Type Flavoring Composition

[0041] 0.2 ppm of (2E,7Z)-2,4,7-decatrienal (4Z:4E, 75:25) were added toa basic solution of a kiwi flavor (N° 597.944 T; origin: Firmenich SA,Geneva, Switzerland) (1000 ppm) in acidulous sweetened water (7%sucrose, 0.15% citric acid). The thus obtained flavored composition andthe basic solution were compared on a blind test by a panel of expertflavorists. The latter preferred the composition flavored according tothe present invention and mentioned in particular that it provided amore complete mouthfeel, and that its taste was more juicy and moretropical.

Example 5: Mandarin Type Flavoring Composition

[0042] A basic flavoring composition of the mandarin type was preparedwith the following ingredients: Ingredients Parts by weight Methylmethylanthranilate 20 Orange essential oil 980 Total 1000

[0043] To this basic composition, 0.4 parts by weight of (Z)-4-dodecenalwere added to obtain a first composition referred to as composition A;0.4 parts by weight of (2E,4Z,7Z)-2,4,7-decatrienal were added to obtaina second composition referred to as composition B; and finally 0.2 partsby weight of (Z)-4-dodecenal and 0.3 parts by weight of(2E,4Z,7Z)-2,4,7-decatrienal to obtained a third composition referred toas composition C. These three compositions A, B and C were thenevaluated on a blind test, by some expert flavorists. The latterdescribed composition A as having a zest type character, aldehydic,together with a fishy note typical of mandarin; composition B asstrongly reminding tangerine taste, and composition C, which was veryprized by the flavorists, was found to mix in a very pleasant way thefatty and aldehydic character and the oily, fishy notes of mandarin andtangerine, thus providing a natural and juicy mixture.

What is claimed is:
 1. A process to confer, improve, enhance or modify amandarin or tangerine character of a composition or product, wherein aperceptible amount of the compound of formula (I)

wherein the double bond in position 4 has a cis or trans configuration,or of a mixture of these compounds, is added to the composition orproduct.
 2. Process according to claim 1, wherein the compound offormula (I) is present in combination with (Z)-4-dodecenal.
 3. Themethod of claim 1, wherein the compound is (2E,4Z,7Z)-2,4,7-decatrienal.4. The method of claim 1, wherein the compound is a mixture of(2E,4Z,7Z)-2,4,7-decatrienal and (2E,4E,7Z)-2,4,7-decatrienal containinga preponderant amount of (2E,4Z,7Z)-2,4,7-decatrienal.
 5. The method ofclaim 3, wherein the amount of (2E,4Z,7Z)-2,4,7-decatrienal is at least75%.
 6. A method of preparing a perfuming composition or a perfumedproduct which comprises adding to the composition or product anolfactory perceptible amount of a compound of formula

wherein the double bond in position 4 has a cis or trans configuration,or of a mixture of these compounds, in order to provide an odor note (a)having a linseed oil character which is more perceptible than aldehydeconnotation or (b) of a natural mandarin note.
 7. The method of claim 6,wherein the compound is (2E,4Z,7Z)-2,4,7-decatrienal.
 8. The method ofclaim 6, wherein the compound is a mixture of(2E,4Z,7Z)-2,4,7-decatrienal and (2E,4E,7Z)-2,4,7-decatrienal containinga preponderant amount of (2E,4Z,7Z)-2,4,7-decatrienal.
 9. The method ofclaim 8, wherein the amount of (2E,4Z,7Z)-2,4,7-decatrienal is at least75%.
 10. A perfuming composition or perfumed product containing asactive ingredient a compound of formula (I) as defined in claim
 6. 11. Aperfumed product containing as active ingredient a compound of formula(I) as defined in claim 6 and being in the form of a perfume or aCologne, a soap, a bath or shower gel, a shampoo or other hair-careproduct, a cosmetic preparation, a body deodorant or an air freshener, adetergent or a fabric softener, or a household product.
 12. Perfumingcomposition or perfumed product according to claim 10, wherein theactive ingredient is present in an amount to impart a mandarin ortangerine character to the composition or product.
 13. A method ofreconstituting a mandarin or tangerine flavor in a composition orproduct, which comprises adding thereto a flavor perceptible amount of acompound of formula

wherein the double bond in position 4 has a cis or trans configuration,or of a mixture of these compounds, in order to develop a gustatory noteof such flavor with the flavor having a natural character.
 14. Themethod of claim 13, wherein the compound is(2E,4Z,7Z)-2,4,7-decatrienal.
 15. The method of claim 13, wherein thecompound is a mixture of (2E,4Z,7Z)-2,4,7-decatrienal and(2E,4E,7Z)-2,4,7-decatrienal containing a preponderant amount of(2E,4Z,7Z)-2,4,7-decatrienal.
 16. The method of claim 15, wherein theamount of (2E,4Z,7Z)-2,4,7-decatrienal is at least 75%.
 17. A flavouringcomposition or flavored product containing as active ingredient acompound of formula (I) such as defined in claim
 13. 18. A flavoringcomposition or flavored product containing as active ingredient acompound of formula (I) such as defined in claim 13 and also containing(Z)-4-dodecenal as an active co-ingredient.
 19. The flavoringcomposition or flavored product according to claim 18, wherein thecompound of formula (I) is present at a concentration of between 0.01ppm and 0.5 ppm.
 20. A flavored product containing as active ingredienta compound of formula (I) such as defined in claim 13 and being in theform of a food or a beverage, a chewing-gum or a pharmaceuticalpreparation.